The invention relates to compositions containing a) one or more substances selected from the group of hydrogen peroxide and substances releasing hydrogen peroxide, b) water, d) one or more substances selected from the group consisting of hydroxypyridones and the salts thereof, characterized in that said compositions do not comprise polymers having thickening properties. The compositions are particularly characterized by the advantageous storage stability thereof.
|
1. A composition comprising
a) at least one substance selected from the group consisting of hydrogen peroxide and hydrogen peroxide-releasing substances,
b) water, and
d) at least one substance selected from the group consisting of compounds of the formula (I) and salts thereof
e####
##STR00002##
in which R1 is H or a C1-C4 alkyl radical and R2 is H, an unsubstituted or halogen-substituted, branched or unbranched C1-C20 alkyl radical, an unsubstituted or halogen-substituted C5-C8 cycloalkyl radical, an unsubstituted or halogen-substituted C6-C10 aryl radical or an unsubstituted or halogen-substituted, branched or unbranched C7-C20 aralkyl radical,
wherein the composition further comprises active antimicrobial ingredients in amounts from 0.001% to 5.0% by weight, based on the total weight of the composition,
with the proviso that the composition does not comprise any polymer having thickening properties.
2. The composition as claimed in
3. The composition as claimed in
4. The composition as claimed in
5. The composition as claimed in
6. The composition as claimed in
7. The composition as claimed in
11. A composition for oxidative bleaching of fibers or textiles comprising at least one composition according to
|
|||||||||||||||||||||||||||||||||||||
The present invention relates to compositions comprising hydrogen peroxide or hydrogen peroxide-releasing substances.
Aqueous compositions comprising hydrogen peroxide are utilized in various applications. They are used in cosmetic compositions, for example as a bleaching composition for hair, as a developer component in hair dyes, but also as a component for hair setting in permanent wave formulations. Further applications are, for example, tooth bleaching compositions. In industrial cleaning and in domestic cleaning and in textile bleaching too, acidic, hydrogen peroxide-containing compositions are present in cleaner formulations.
However, the stability of the hydrogen peroxide or of the hydrogen peroxide-releasing substances in compositions which do not comprise any thickening polymers is often unsatisfactory.
The literature cites various stabilizers for hydrogen peroxide; for example, EP 1 347 736 discloses oxidative compositions for hair treatment, these comprising stabilizers based on pyrophosphate, stannates, phenacetin or oxyquinoline, or combinations thereof. However, these compositions also comprise polymers having thickening properties.
It was therefore an object of the present invention to provide compositions of long-term storage stability which comprise hydrogen peroxide and/or hydrogen peroxide-releasing substances, but no polymers having thickening properties.
It has now been found that, surprisingly, this object is achieved by incorporating hydroxypyridones or salts thereof into aqueous compositions which comprise one or more substances selected from the group consisting of hydrogen peroxide and hydrogen peroxide-releasing substances but do not comprise any polymers having thickening properties.
The invention therefore provides compositions comprising
The inventive compositions now also make it possible to obtain low-viscosity compositions comprising hydrogen peroxide and/or hydrogen peroxide-releasing substances with elevated stability. Low-viscosity compositions are required, for example, in the sector of cleaner formulations or else of textile bleaching. The increased stability of the hydrogen peroxide and/or of the hydrogen peroxide-releasing substances in these compositions can achieve improved cleaning or bleaching performance.
Preferably, the one or more substances of component a) are selected from the group consisting of hydrogen peroxide, urea peroxide, perborates, persulfates and mixtures thereof. More preferably, the substance of component a) is hydrogen peroxide.
The one or more substances selected from the group consisting of hydrogen peroxide and hydrogen peroxide-releasing substances of component a) are present in the inventive compositions preferably in amounts of 0.5 to 20% by weight, more preferably in amounts of 1 to 10% by weight, especially preferably in amounts of 1.5 to 7% by weight and exceptionally preferably in amounts of 2 to 7% by weight, based on the total weight of the compositions. Among these, the substance of component a) is again preferably hydrogen peroxide, which is present in the inventive compositions preferably in amounts of 0.5 to 20% by weight, more preferably in amounts of 1 to 10% by weight, especially preferably in amounts of 1.5 to 7% by weight and exceptionally preferably in amounts of 2 to 7% by weight, based on the total weight of the compositions.
In a preferred embodiment of the invention, the water (component b)) is present in the inventive compositions in an amount of 40% by weight or more and preferably in an amount of 50% by weight or more, based on the total weight of the compositions.
Polymers having thickening properties are, in the context of the present invention, preferably understood to mean polymeric materials which have a molecular weight above 5000 g/mol and are suitable for significantly thickening a composition comprising one or more substances selected from the group consisting of hydrogen peroxide and hydrogen peroxide-releasing substances with use amounts of the polymer of 30% by weight or less, preferably of 10% by weight or less, more preferably of 6% by weight or less and especially preferably of 3% by weight or less, based on the total weight of the composition. This thickening is preferably such that the viscosity of the composition in mPa·s at 20° C. is increased by 30% or more with the abovementioned amounts of the polymers.
The viscosity of the inventive compositions is preferably ≦2000 mPa·s at 20° C., more preferably ≦1000 mPa·s at 20° C. and especially preferably ≦500 mPa·s at 20° C. The viscosities are measured on the inventive compositions themselves with a Brookfield viscometer model DV II at 20 revolutions/minute and 20° C. The spindles from the RV spindle set are used. Under these measurement conditions, spindle 1 is selected for viscosities not exceeding 500 mPa·s, spindle 2 for viscosities not exceeding 1000 mPa·s, and spindle 3 for viscosities not exceeding 5000 mPa·s.
Preferably, the inventive compositions do not comprise any polymers.
Preferably, the one or more substances of component d) are selected from compounds of the formula (I) and salts thereof
##STR00001##
in which R1 is H or a C1-C4 alkyl radical and R2 is H, an unsubstituted or halogen-substituted, branched or unbranched C1-C20 alkyl radical, an unsubstituted or halogen-substituted C5-C8 cycloalkyl radical, an unsubstituted or halogen-substituted C6-C10 aryl radical or an unsubstituted or halogen-substituted, branched or unbranched C7-C20 aralkyl radical.
The R2 radicals are preferably not halogen-substituted.
In a preferred embodiment of the invention, the one or more compounds of component d) are present in the inventive compositions in the form of the acid (compounds of the formula (I)) or in the form of the alkali metal, alkaline earth metal or amine salts thereof, or salts thereof with polymeric counterions.
R1 in the one or more compounds of the formula (I) or in the salts thereof is preferably methyl, and R2 is preferably cyclohexyl or 2,4,4-trimethylpentyl.
More preferably, the compounds of the formula (I) are in the form of the alkanolamine salts thereof and especially preferably in the form of the monoethanolamine salts thereof. Examples of such salts are mentioned in DE 2234009.
Particular preference is given to 4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone, the monoethanolamine salt of 4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone (Octopirox®, Clariant), and 4-methyl-6-(cyclohexyl)-1-hydroxy-2-pyridone and the monoethanolamine salt of 4-methyl-6-(cyclohexyl)-1-hydroxy-2-pyridone (Ciclopirox®, Sanofi-Aventis).
These substances can be obtained by methods known from the literature; cf. the references cited in DE 2234009.
In the inventive compositions, the one or more substances of component d) are present in amounts of preferably 0.1 to 20 000 ppm (0.00001 to 2% by weight), more preferably in amounts of 0.5 to 1000 ppm (0.00005 to 0.1% by weight) and especially preferably in amounts of 0.5 to 100 ppm (0.00005 to 0.01% by weight), based on the total weight of the compositions.
The hydroxypyridones can be combined in the inventive compositions with further stabilizers. Further suitable stabilizers are, for example, polyphosphates and the alkali metal or alkaline earth metal salts thereof, alkali metal or alkaline earth metal stannates, phenacetin and the acid salts thereof, and oxyquinoline and the acid salts thereof. In general, the hydrogen peroxide solutions ready for delivery already comprise stabilizers, preferably in the form of polyphosphates.
The inventive compositions can be used as bleaching compositions for hair or teeth, as a bleaching component or developer for oxidative hair dyes or as a fixing component for permanent wave formulations and as a domestic cleaner. In addition, the inventive compositions can be used, for example, as prewash sprays, stain removers, surface cleaners or toilet cleaners. A further possible use is that of hair coloring compositions for prevention of bleaching damage in the course of hair coloring.
In a further preferred embodiment of the invention, the inventive compositions are emulsions. The emulsions are preferably oil-in-water emulsions or microemulsions.
The nonaqueous component of these emulsions, which is composed substantially of the emulsifier and the oil body, is typically 0.5 to 20.0% by weight and preferably 1.0 to 10.0% by weight, based on the total weight of the emulsions. It follows from this that the emulsions may contain 80.0 to 99.5% by weight and preferably 90.0 to 99.0% by weight of the aqueous phase, based on the total weight of the emulsions.
The inventive compositions may also comprise anionic, cationic, nonionic, ampholytic surfactants and/or betaine surfactants.
The total amount of the surfactants used in the inventive compositions is, based on the total weight of the compositions, preferably from 0.1 to 20% by weight, more preferably from 0.5 to 10.0% by weight and especially preferably from 1.0 to 5.0% by weight.
Preferred anionic surfactants are (C10-C22)-alkyl and -alkylene carboxylates, alkyl ether carboxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, alkylamide sulfates and sulfonates, alkanesulfonates and hydroxyalkanesulfonates, olefinsulfonates, acyl esters of isethionates, α-sulfo fatty acid esters, alkylbenzenesulfonates, alkylphenol glycol ether sulfonates, sulfosuccinates, sulfosuccinic monoesters and diesters, fatty alcohol phosphates, fatty alcohol ether phosphates, protein-fatty acid condensation products, alkyl monoglyceride sulfates and sulfonates, alkyl glyceride ether sulfonates, fatty acid methyl taurides, fatty acid sarcosinates, sulforicinoleates, acyl glutamates and acyl glycinates. These compounds and mixtures thereof are utilized in the form of the water-soluble or water-dispersible salts thereof, for example the sodium, potassium, magnesium, ammonium, mono-, di- and triethanolammonium, and analogous alkylammonium salts.
The amount of the anionic surfactants in the inventive compositions is preferably from 0.05 to 20.0% by weight, more preferably from 0.5 to 10.0% by weight and especially preferably from 1.0 to 5.0% by weight, based on the total weight of the compositions.
Preferred cationic surfactants are quaternary ammonium salts, such as di(C8-C22)-alkyldimethylammonium chloride or bromide, preferably di(C8-C22)-alkyldimethylammonium chloride or bromide; (C8-C22)-alkyl-dimethylethylammonium chloride or bromide; (C8-C22)-alkyltrimethylammonium chloride or bromide, preferably cetyltrimethylammonium chloride or bromide and (C8-C22)-alkyltrimethylammonium chloride or bromide; (C10-C24)-alkyldimethylbenzylammonium chloride or bromide, preferably (C12-C18)-alkyldimethylbenzylammonium chloride, (C8-C22)-alkyl-dimethylhydroxyethylammonium chloride, phosphate, sulfate or lactate, (C8-C22)-alkylamidopropyltrimethylammonium chloride or methosulfate, N,N-bis(2-C8-C22-alkanoyloxyethyl)dimethylammonium chloride or methosulfate, N,N-bis(2-C8-C22-alkanoyloxyethyl)hydroxyethylmethyl-ammonium chloride or methosulfate, and ester quats based on C8-C22 alkanoyl esters of triethanolamine or methyldiethanolamine.
The amount of the cationic surfactants in the inventive compositions is preferably from 0.1 to 10.0% by weight, more preferably from 0.5 to 7.0% by weight and especially preferably from 1.0 to 5.0% by weight, based on the total weight of the compositions.
Preferred nonionic surfactants are, for example, fatty acid alkanolamides; sucrose esters; sorbitol esters and sorbitan esters, and also C8-C22-alkyl polyglucosides.
The amount of the nonionic surfactants in the inventive compositions (for example in the case of rinse-off products) is preferably in the range from 0.05 to 20.0% by weight, more preferably from 0.1 to 10.0% by weight and especially preferably from 0.5 to 5.0% by weight, based on the total weight of the compositions.
In addition, the inventive compositions may comprise amphoteric surfactants. These can be described as derivatives of long-chain secondary or tertiary amines which have an alkyl group with 8 to 18 carbon atoms and in which a further group is substituted by an anionic group which imparts solubility in water, thus, for example, by a carboxyl, sulfate or sulfonate group. Preferred amphoteric surfactants are N—(C12-C18)-alkyl-β-amino-propionates and N—(C12-C18)-alkyl-β-iminodipropionates as alkali metal and mono-, di- and trialkylammonium salts; suitable further surfactants are also amine oxides. These are oxides of tertiary amines with a long-chain group having 8 to 18 carbon atoms and two mostly short-chain alkyl groups having 1 to 4 carbon atoms. Preference is given here, for example, to the C10- to C18-alkyldimethylamine oxides, fatty acid amidoalkyldimethylamine oxide.
A further preferred group of surfactants is that of betaine surfactants, also known as zwitterionic surfactants. These contain, in the same molecule, a cationic group, especially an ammonium group, and an anionic group, which may be a carboxylate group, sulfate group or sulfonate group. Suitable betaines are preferably alkylbetaines such as cocobetaine or fatty acid alkylamidopropyl betaines, for example cocoacylamidopropyl dimethyl betaine or the C12- to C18-dimethylaminohexanoates and/or the C10- to C18-acylamidopropane dimethyl betaines.
The amount of the amphoteric surfactants and/or betaine surfactants in the inventive compositions is preferably from 0.5 to 20.0% by weight and more preferably from 1.0 to 10.0% by weight, based on the total weight of the compositions.
Preferred surfactants are lauryl sulfate, laureth sulfate, cocoamidopropyl betaine, alkyl betaines such as cocobetaine, amine oxides, sodium cocoylglutamate and lauroamphoacetate.
The inventive compositions may comprise, as further assistants and additives, for example, oil bodies, waxes, emulsifiers, coemulsifiers, solubilizers, superfatting agents, refatting agents, active antimicrobial ingredients, humectants, solvents, dyes, fragrances, pearlizing agents and/or opacifiers.
The oil bodies may advantageously be selected from the groups of triglycerides, natural and synthetic fatty substances, preferably esters of fatty acids with alcohols of low carbon number, for example with isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low carbon number or with fatty acids or from the group of alkyl benzoates, and also natural or synthetic hydrocarbon oils.
Useful substances include triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated, C8-C30-fatty acids, in particular vegetable oils, such as sunflower oil, corn oil, soybean oil, rice oil, jojoba oil, babassu oil, pumpkin oil, grapeseed oil, sesame oil, walnut oil, apricot oil, orange oil, wheatgerm oil, peach kernel oil, macadamia oil, avocado oil, sweet almond oil, lady's smock oil, castor oil, olive oil, peanut oil, rapeseed oil and coconut oil, and also synthetic triglyceride oils, e.g. the commercial product Myritol® 318. Hydrogenated triglycerides are also preferred in accordance with the invention. Oils of animal origin, for example beef tallow, perhydrosqualene, lanolin, can also be used.
A further class of preferred oil bodies is that of the benzoic esters of linear or branched C8-22-alkanols, e.g. the commercial products Finsolv® SB (isostearyl benzoate), Finsolv® TN (C12-C15-alkyl benzoate) and Finsolv® EB (ethylhexyl benzoate).
A further class of preferred oil bodies is that of the dialkyl ethers having a total of 12 to 36 carbon atoms, especially having 12 to 24 carbon atoms, for example di-n-octyl ether (Cetiol® OE), di-n-nonyl ether, di-n-decyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether and n-hexyl n-undecyl ether, di-3-ethyldecyl ether, tert-butyl n-octyl ether, isopentyl n-octyl ether and 2-methylpentyl n-octyl ether, and di-tert-butyl ether and diisopentyl ether.
Likewise useful are branched saturated or unsaturated fatty alcohols having 6-30 carbon atoms, e.g. isostearyl alcohol, and Guerbet alcohols.
A further class of preferred oil bodies is that of alkyl hydroxycarboxylates. Preferred alkyl hydroxycarboxylates are full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further esters of hydroxy-carboxylic acids which are suitable in principle are esters of β-hydroxy-propionic acid, of tartronic acid, of D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols having 8 to 22 carbon atoms. The esters of C12-C15-fatty alcohols are particularly preferred. Esters of this type are commercially available, e.g. under the trade name Cosmacol® from EniChem, Augusta Industriale.
A further class of preferred oil bodies is that of dicarboxylic esters of linear or branched C2-C10-alkanols, such as di-n-butyl adipate (Cetiol® B), di(2-ethylhexyl) adipate and di(2-ethylhexyl) succinate, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate, and also diisotridecyl azelate.
Likewise preferred oil bodies are symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, glycerol carbonate or dicaprylyl carbonate (Cetiol® CC).
A further class of preferred oil bodies is that of the esters of dimers of unsaturated C12-C22-fatty acids (dimer fatty acids) with monovalent linear, branched or cyclic C2-C18-alkanols or with polyvalent linear or branched C2-C6-alkanols.
A further class of preferred oil bodies is that of hydrocarbon oils, for example those with linear or branched, saturated or unsaturated C7-C40-carbon chains, for example Vaseline, dodecane, isododecane, cholesterol, lanolin, synthetic hydrocarbons, hexadecane, isohexadecane, paraffin oils, isoparaffin oils, e.g. the commercial products of the Permethyl® series, squalane, squalene, and alicyclic hydrocarbons, e.g. the commercial product 1,3-di(2-ethylhexyl)cyclohexane (Cetiol® S), ozokerite, and ceresine.
The inventive compositions may comprise waxes, for example paraffin waxes, microwaxes and ozokerites, beeswax and its component fractions, beeswax derivatives, and natural waxes such as rice wax, candelilla wax, carnauba wax, japan wax or shellac wax.
Emulsifiers, coemulsifiers and solubilizers which may be used are nonionic, anionic, cationic or amphoteric surface-active compounds.
Useful nonionogenic surface-active compounds are preferably:
fatty alcohols having 8 to 22 carbon atoms, glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms; polyol esters; fatty acid amides, fatty acid alkanolamides and mixtures of compounds of two or more of these substance classes.
Suitable ionogenic coemulsifiers are, for example, anionic emulsifiers, such as mono-, di- or triphosphoric acid esters, soaps (e.g. sodium stearate), fatty alcohol sulfates, but also cationic emulsifiers such as mono-, di- and trialkyl quats.
Available amphoteric emulsifiers are preferably alkylaminoalkylcarboxylic acids, betaines, sulfo betaines and imidazoline derivatives.
Particularly advantageous coemulsifiers are glyceryl monostearate, glyceryl monooleate, diglyceryl monostearate, glyceryl isostearate, glycol distearate, sorbitan monoisostearate, sorbitan stearate, sorbitan oleate, sucrose distearate, lecithin, cetyl alcohol, stearyl alcohol, behenyl alcohol and isobehenyl alcohol.
The inventive compositions may comprise one or more of the emulsifiers, coemulsifiers or solubilizers in amounts of 0.1 to 20.0% by weight, preferably of 1.0 to 15.0% by weight and more preferably of 3.0% to 10.0% by weight, based on the total weight of the compositions.
Superfatting agents which may be used are preferably lanolin and lecithin, nonethoxylated lanolin derivatives and lecithin derivatives or acylated lanolin derivatives and lecithin derivatives, polyol fatty acid esters, mono-, di- and triglycerides and/or fatty acid alkanolamides, where the latter simultaneously serve as foam stabilizers, which are preferably used in amounts of 0.01% to 10.0% by weight, more preferably of 0.1% to 5.0% by weight and especially preferably of 0.5% to 3.0% by weight, based on the total weight of the compositions.
Antimicrobial active ingredients which may be used are cetyltrimethylammonium chloride, cetylpyridinium chloride, benzethonium chloride, diisobutylethoxyethyldimethylbenzylammonium chloride, sodium aluminum chlorohydroxylactate, triethyl citrate, 2,4,4′-trichloro-2′-hydroxydiphenyl ether (triclosan), 3,4,4′-trichlorocarbanilide (triclocarban), diaminoalkyl-amide, for example L-lysine hexadecylamide, citrate heavy metal salts, salicylates, pyrithiones and heavy metal salts thereof, especially zinc pyrithione, farnesol, ketoconazole, oxiconazole, bifonazole, butoconazole, cloconazole, clotrimazole, econazole, enilconazole, fenticonazole, isoconazole, miconazole, sulconazole, tioconazole, fluconazole, itraconazole, terconazole, naftifine and terbinafine, selenium disulfide, iodopropynyl butylcarbamate, methylchloroisothiazolinone, methyl-isothiazolinone, methyldibromoglutaronitrile, AgCl, chloroxylenol, sodium benzoate, and phenoxyethanol, phenoxyisopropanol, parabens, preferably butyl, ethyl, methyl and propyl paraben, and sodium salts thereof, pentanediol, 1,2-hexanediol, 1,2-octanediol, 2-bromo-2-nitropropane-1,3-diol, ethylhexylglycerol, benzyl alcohol, sorbic acid, benzoic acid, lactic acid, imidazolidinylurea, diazolidinylurea, dimethyloldimethylhydantoin (DMDMH), sodium salt of hydroxymethylglycinate.
The inventive compositions comprise the active antimicrobial ingredients preferably in amounts from 0.001% to 5.0% by weight, more preferably from 0.01% to 3.0% by weight, and with particular preference from 0.1% to 2.0% by weight, based on the total weight of the compositions.
In addition, it is possible to use humectants selected from the sodium salt of 2-pyrrolidone-5-carboxylate (NaPCA), guanidine; glycolic acid and salts thereof, lactic acid and salts thereof, glucosamines and salts thereof, lactamide monoethanolamine, acetamide monoethanolamine, urea, hydroxy acids, panthenol and derivatives thereof, for example D-panthenol (R-2,4-dihydroxy-N-(3-hydroxypropyl)-3,3-dimethylbutamide), DL-panthenol, calcium pantothenate, panthetine, pantotheine, panthenyl ethyl ether, isopropyl palmitate, glycerol and/or sorbitol, preferably in amounts of from 0.1% to 15.0% by weight and particularly preferably from 0.5% to 5.0% by weight, based on the total weight of the compositions.
Additionally, the inventive compositions may comprise organic solvents. In principle, suitable organic solvents are all mono- or polyhydric alcohols. Preference is given to using alcohols having 1 to 4 carbon atoms, such as ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, glycerol, 1,2-propanediol and 1,3-propanediol, and mixtures of said alcohols. Further suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
The inventive compositions may comprise dyes and pigments, either organic or inorganic dyes selected from the corresponding positive list of the German Cosmetics Act or from the EC list of cosmetic colorants.
Chemical or other name
CIN
Color
Pigment Green
10006
green
Acid Green 1
10020
green
2,4-Dinitrohydroxynaphthalene-7-sulfonic acid
10316
yellow
Pigment Yellow 1
11680
yellow
Pigment Yellow 3
11710
yellow
Pigment Orange 1
11725
orange
2,4-Dihydroxyazobenzene
11920
orange
Solvent Red 3
12010
red
1-(2′-Chloro-4′-nitro-1′-phenylazo)-2-hydroxy-
12085
red
naphthalene
Pigment Red 3
12120
red
Cerise Red; Sudan Red; Fat Red G
12150
red
Pigment Red 112
12370
red
Pigment Red 7
12420
red
Pigment Brown 1
12480
brown
4-(2′-Methoxy-5′-sulfonic acid diethylamide-
12490
red
1′-phenylazo)-3-hydroxy-5″-chloro-2″,4″-dimethoxy-
2-naphthanilide
Disperse Yellow 16
12700
yellow
1-(4-Sulfo-1-phenylazo)-4-aminobenzenesulfonic acid
13015
yellow
2,4-Dihydroxyazobenzene-4′-sulfonic acid
14270
orange
2-(2,4-Dimethylphenylazo-5-sulfonic acid)-1-hydroxy-
14700
red
naphthalene-4-sulfonic acid
2-(4-Sulfo-1-naphthylazo)-1-naphthol-4-sulfonic acid
14720
red
2-(6-Sulfo-2,4-xylylazo)-1-naphthol-5-sulfonic acid
14815
red
1-(4′-Sulfophenylazo)-2-hydroxynaphthalene
15510
orange
1-(2-Sulfonic acid-4-chloro-5-carboxylic acid-
15525
red
1-phenylazo)-2-hydroxynaphthalene
1-(3-Methylphenylazo-4-sulfonic acid)-2-hydroxy-
15580
red
naphthalene
1-(4′,(8′)-Sulfonic acid naphthylazo)-2-hydroxy-
15620
red
naphthalene
2-Hydroxy-1,2′-azonaphthalene-1′-sulfonic acid
15630
red
3-Hydroxy-4-phenylazo-2-naphthylcarboxylic acid
15800
red
1-(2-Sulfo-4-methyl-1-phenylazo)-2-naphthylcarboxylic
15850
red
acid
1-(2-Sulfo-4-methyl-5-chloro-1-phenylazo)-2-hydroxy-
15865
red
naphthalene-3-carboxylic acid
1-(2-Sulfo-1-naphthylazo)-2-hydroxynaphthalene-
15880
red
3-carboxylic acid
1-(3-Sulfo-1-phenylazo)-2-naphthol-6-sulfonic acid
15980
orange
1-(4-Sulfo-1-phenylazo)-2-naphthol-6-sulfonic acid
15985
yellow
Allura Red
16035
red
1-(4-Sulfo-1-naphthylazo)-2-naphthol-3,6-disulfonic
16185
red
acid
Acid Orange 10
16230
orange
1-(4-Sulfo-1-naphthylazo)-2-naphthol-6,8-disulfonic
16255
red
acid
1-(4-Sulfo-1-naphthylazo)-2-naphthol-3,6,8-trisulfonic
16290
red
acid
8-Amino-2-phenylazo-1-naphthol-3,6-disulfonic acid
17200
red
Acid Red 1
18050
red
Acid Red 155
18130
red
Acid Yellow 121
18690
yellow
Acid Red 180
18736
red
Acid Yellow 11
18820
yellow
Acid Yellow 17
18965
yellow
4-(4-Sulfo-1-phenylazo)-1-(4-sulfophenyl)-5-hydroxy-
19140
yellow
pyrazolone-3-carboxylic acid
Pigment Yellow 16
20040
yellow
2,6-(4′-Sulfo-2″,4″-dimethyl)bisphenylazo)-
20170
orange
1,3-dihydroxybenzene
Acid Black 1
20470
black
Pigment Yellow 13
21100
yellow
Pigment Yellow 83
21108
yellow
Solvent Yellow
21230
yellow
Acid Red 163
24790
red
Acid Red 73
27290
red
2-[4′-(4″-Sulfo-1″-phenylazo)-7′-sulfo-1′-naphthylazo]-
27755
black
1-hydroxy-7-aminonaphthalene-3,6-disulfonic acid
4′-[(4″-Sulfo-1″-phenylazo)-7′-sulfo-1′-naphthylazo]-
28440
black
1-hydroxy-8-acetylaminonaphthalene-3,5-disulfonic
acid
Direct Orange 34, 39, 44, 46, 60
40215
orange
Food Yellow
40800
orange
trans-β-Apo-8′-Carotenealdehyde (C30)
40820
orange
trans-Apo-8′-Carotenic acid (C30)-ethyl ester
40825
orange
Canthaxanthin
40850
orange
Acid Blue 1
42045
blue
2,4-Disulfo-5-hydroxy-4′-4″-bis(diethylamino)triphenyl-
42051
blue
carbinol
4-[(4-N-Ethyl-p-sulfobenzylamino)phenyl-(4-hydroxy-
42053
green
2-sulfophenyl)(methylene)-1-(N-ethyl-N-p-sulfobenzyl)-
2,5-cyclohexadieneimine]
Acid Blue 7
42080
blue
(N-Ethyl-p-sulfobenzylaminophenyl-(2-sulfophenyl)-
42090
blue
methylene-(N-ethyl-N-p-sulfobenzyl)cyclohexa-
dieneimine
Acid Green 9
42100
green
Diethyldisulfobenzyldi-4-amino-2-chlorodi-2-methyl-
42170
green
fuchsonimmonium
Basic Violet 14
42510
violet
Basic Violet 2
42520
violet
2′-Methyl-4′-(N-ethyl-N-m-sulfobenzyl)amino-
42735
blue
4″-(N-diethyl)amino-2-methyl-N-ethyl-N-m-sulfobenzyl-
fuchsonimmonium
4′-(N-Dimethyl)amino-4″-(N-phenyl)aminonaphtho-
44045
blue
N-dimethylfuchsonimmonium
2-Hydroxy-3,6-disulfo-4,4′-bisdimethylaminonaphtho-
44090
green
fuchsinimmonium
Acid red
45100
red
3-(2′-Methylphenylamino)-6-(2′-methyl-4′-sulfophenyl-
45190
violet
amino)-9-(2″-carboxyphenyl)xanthenium salt
Acid Red 50
45220
red
Phenyl-2-oxyfluorone-2-carboxylic acid
45350
yellow
4,5-Dibromofluorescein
45370
orange
2,4,5,7-Tetrabromofluorescein
45380
red
Solvent Dye
45396
orange
Acid Red 98
45405
red
3′,4′,5′,6′-Tetrachloro-2,4,5,7-tetrabromofluorescein
45410
red
4,5-Diiodofluorescein
45425
red
2,4,5,7-Tetraiodofluorescein
45430
red
Quinophthalone
47000
yellow
Quinophthalonedisulfonic acid
47005
yellow
Acid Violet 50
50325
violet
Acid Black 2
50420
black
Pigment Violet 23
51319
violet
1,2-Dioxyanthraquinone, calcium-aluminum complex
58000
red
3-Oxypyrene-5,8,10-sulfonic acid
59040
green
1-Hydroxy-4-N-phenylaminoanthraquinone
60724
violet
1-Hydroxy-4-(4′-methylphenylamino)anthraquinone
60725
violet
Acid Violet 23
60730
violet
1,4-Di(4′-methylphenylamino)anthraquinone
61565
green
1,4-Bis(o-sulfo-p-toluidine)anthraquinone
61570
green
Acid Blue 80
61585
blue
Acid Blue 62
62045
blue
N,N′-Dihydro-1,2,1′,2′-anthraquinoneazine
69800
blue
Vat Blue 6; Pigment Blue 64
69825
blue
Vat Orange 7
71105
orange
Indigo
73000
blue
Indigodisulfonic acid
73015
blue
4,4′-Dimethyl-6,6′-dichlorothioindigo
73360
red
5,5′-Dichloro-7,7′-dimethylthioindigo
73385
violet
Quinacridone Violet 19
73900
violet
Pigment Red 122
73915
red
Pigment Blue 16
74100
blue
Phthalocyanine
74160
blue
Direct Blue 86
74180
blue
Chlorinated phthalocyanines
74260
green
Natural Yellow 6, 19; Natural Red 1
75100
yellow
Bixin, Nor-Bixin
75120
orange
Lycopene
75125
yellow
trans-alpha, beta- or gamma-Carotene
75130
orange
Keto and/or hydroxyl derivatives of carotene
75135
yellow
Guanine or pearlescent agents
75170
white
1,7-Bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-
75300
yellow
3,5-dione
Complex salt (Na, Al, Ca) of carminic acid
75470
red
Chlorophyll a and b; copper compounds of the
75810
green
chlorophylls and chlorophyllines
Aluminum
77000
white
Aluminum hydrate
77002
white
Water-containing aluminum silicates
77004
white
Ultramarine
77007
blue
Pigment Red 101 and 102
77015
red
Barium sulfate
77120
white
Bismuth oxychloride and its mixtures with mica
77163
white
Calcium carbonate
77220
white
Calcium sulfate
77231
white
Carbon
77266
black
Pigment Black 9
77267
black
Carbo medicinalis vegetabilis
77268:1
black
Chromic oxide
77288
green
Chromium oxide, hydrated
77289
green
Pigment Blue 28, Pigment Green 14
77346
green
Pigment Metal 2
77400
brown
Gold
77480
brown
Iron oxides and hydroxides
77489
orange
Iron oxides and hydroxides
77491
red
Hydrated iron oxide
77492
yellow
Iron oxide
77499
black
Mixtures of iron(II) and iron(III) hexacyanoferrate
77510
blue
Pigment White 18
77713
white
Manganese ammonium diphosphate
77742
violet
Manganese phosphate; Mn3(PO4)2•7H2O
77745
red
Silver
77820
white
Titanium dioxide and its mixtures with mica
77891
white
Zinc oxide
77947
white
6,7-Dimethyl-9-(1′-D-ribityl)isoalloxazine, lactoflavin
yellow
Caramel
brown
Capsanthin, Capsorubin
orange
Betanine
red
Benzopyrilium salts, anthocyanines
red
Aluminum, zinc, magnesium and calcium stearate
white
Bromothymol Blue
blue
Bromocresol Green
green
Acid Red 195
red
Also advantageous are oil-soluble natural dyes, for example paprika extracts, β-carotene and cochineal.
Fragrance and/or perfume oils which may be used are individual odorant compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types. Odorant compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ethers, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellol, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the ionones, alpha-isomethylionone and methyl cedryl ketone, the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, and the hydrocarbons include primarily the terpenes and balsams. Preference is given to using mixtures of different odorants which together produce a pleasing scent note.
Perfume oils may also comprise natural odorant mixtures, as are accessible from vegetable or animal sources, e.g. pine oil, citrus oil, jasmine oil, lily oil, rose oil or ylang-ylang oil. Essential oils of relatively low volatility which are usually used as aromatic components are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil and ladanum oil.
Preferentially suitable pearlizing components are fatty acid monoalkanol-amides, fatty acid dialkanolamides, monoesters or diesters of alkylene glycols, in particular ethylene glycol and/or propylene glycol, with higher fatty acids, such as, for example, palmitic acid, stearic acid and behenic acid, monoesters or polyesters of glycerol with carboxylic acids, fatty acids and metal salts thereof, ketosulfones or mixtures of the specified compounds. Particular preference is given to ethylene glycol distearates and/or polyethylene glycol distearates having an average of 3 glycol units.
If the inventive compositions comprise pearlizing compounds, these are preferably present in the inventive compositions in an amount of 0.1 to 15.0% by weight and more preferably in an amount of 1.0 to 10.0% by weight, based on the total weight of the compositions.
The acids or alkalis used for pH adjustment are preferably mineral acids, more particularly HCl, inorganic bases, especially NaOH or KOH, and organic acids, especially citric acid.
The inventive compositions preferably have a pH of 2 to 11, more preferably from 7 to 11, more preferably from 8 to 11 and especially preferably from 8.5 to 11.
In a further preferred embodiment of the invention, the inventive compositions are compositions for bleaching and/or coloring of hair or a permanent wave formulation.
In a further preferred embodiment of the invention, the inventive compositions are oxidative cleaner formulations.
In a further preferred embodiment of the invention, the inventive compositions are compositions for oxidative bleaching of fibers or textiles.
The inventive compositions are advantageously suitable for reducing hair damage in hair coloring formulations.
The examples and applications which follow are intended to illustrate the invention in detail, but without restricting it thereto. All percentages are % by weight (% by wt.), unless explicitly stated otherwise.
Hydrogen peroxide solution from Solvay (35% by weight in water) or from Merck (35% by weight in water) was diluted with demineralized water to a hydrogen peroxide content of about 6.0% by weight and adjusted to a pH of 9.0 with sodium hydroxide solution (20% by weight). Further solutions were each additized with 8 ppm of 4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone (additive A, dissolved in propylene glycol). The solutions were stored at room temperature (20° C.) and 40° C. for 1 week and the hydrogen peroxide content was measured before and after storage (see Table 1).
TABLE 1
Results of the measurement of the hydrogen peroxide content
Hydrogen
Hydrogen
Hydrogen
peroxide
peroxide
peroxide
content
content
content
after 1 week
after 1 week
Hydrogen
Additive
immediate
at 20° C.
at 40° C.
peroxide
A
[% by wt.]
[% by wt.]
[% by wt.]
Solvay
no
6.3
4.8
<0.1
(35% by wt.)
Solvay
yes
6.0
6.1
5.9
(35% by wt.)
Merck
no
5.9
3.9
2.0
(35% by wt.)
Merck
yes
6.1
6.1
5.8
(35% by wt.)
Hydrogen peroxide solution from Solvay (35% by weight in water) or from Merck (35% by weight in water), a solution of sodium C14-17 alkyl sec-sulfonates (Hostapur® SAS 30) and demineralized water were mixed so as to result in a hydrogen peroxide content of about 6.0% by weight and a content of sodium C14-17 alkyl sec-sulfonates of 5.0% by weight. Thereafter, sodium hydroxide solution (20% by weight) was used to establish a pH of 9.0. Further solutions were each additized with 7 ppm of 4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone (additive A, dissolved in propylene glycol). The solutions were stored at room temperature and 40° C. for 1 week and the hydrogen peroxide content was measured before and after storage (see Table 2).
TABLE 2
Results of the measurement of the hydrogen peroxide content
Hydrogen
Hydrogen
Hydrogen
peroxide
peroxide
peroxide
content
content
content
after 1 week
after 1 week
Hydrogen
Additive
immediate
at 20° C.
at 40° C.
peroxide
A
[% by wt.]
[% by wt.]
[% by wt.]
Solvay
no
6.1
3.7
0.1
(35% by wt.)
Solvay
yes
6.0
6.1
5.8
(35% by wt.)
Merck
no
5.9
4.2
1.4
(35% by wt.)
Merck
yes
6.0
6.1
5.2
(35% by wt.)
The results of examples 1 and 2 show that 4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone can significantly enhance the storage stability of hydrogen peroxide solutions at high pH both at room temperature and at 40° C.
Ingredient
% by wt.
hydrogen peroxide (35% by wt., aqueous)
10.0
Decyl Glucoside (50% by wt. aqueous solution)
5.0
Coco Glucoside (50% by wt. aqueous solution)
2.0
Hostapur ® SAS 60
5.0
(Sodium C14-17 Alkyl Sec Sulfonate)
4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-
0.0005
pyridone, monoethanolamine salt
propylene glycol
1.0
water
ad 100
Production:
4-Methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone monoethanolamine salt (Octopirox®) is dissolved in propylene glycol. The surfactants are dissolved in water, the hydrogen peroxide solution and the propylene glycol solution are introduced, and the mixture is homogenized. The product is adjusted to pH=4.
Ingredient
% by wt.
hydrogen peroxide (35% by wt., aqueous)
10.0
Sodium C14-17 Olefin Sulfonate
5.0
4-methyl-6-(cyclohexyl)-1-hydroxy-2-pyridone
0.0005
propylene glycol
1.0
water
ad 100
Production:
4-Methyl-6-(cyclohexyl)-1-hydroxy-2-pyridone is dissolved in propylene glycol. The surfactant is dissolved in water, the hydrogen peroxide solution and the propylene glycol solution are introduced, and the mixture is homogenized. The product is adjusted to pH=7.
Ingredient
% by wt.
hydrogen peroxide (35% by wt., aqueous)
12.0
Lauryl Glucoside (50% by wt. aqueous solution)
7.0
4-methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-
0.0005
pyridone
propylene glycol
1.0
MEA dodecylbenzenesulfonate
6.0
water
ad 100
Production:
4-Methyl-6-(2,4,4-trimethylpentyl)-1-hydroxy-2-pyridone is dissolved in propylene glycol.
The surfactants are dissolved in water, the hydrogen peroxide solution and the propylene glycol solution are introduced, and the mixture is homogenized. The product is adjusted to pH=4.7.
Klug, Peter, Pilz, Maurice Frederic, Back, Ute
| Patent | Priority | Assignee | Title |
| 11406582, | Jul 23 2019 | HENKEL AG & CO KGAA | Agent for oxidative lightening and bleaching of the hair |
| Patent | Priority | Assignee | Title |
| 4804705, | Jun 02 1986 | Gel composition | |
| 5206385, | Jan 24 1992 | ISP Investments Inc. | Urea-hydrogen peroxide-polyvinylpyrrolidone process |
| 6083422, | Dec 04 1997 | NOVEON, INC | Thickened bleach compositions |
| 6180118, | Sep 17 1996 | L Oreal | Composition and its uses for the dyeing, permanent reshaping or bleaching of the hair |
| 20040074015, | |||
| 20040191202, | |||
| 20060009371, | |||
| 20070199160, | |||
| 20110003010, | |||
| 20130236383, | |||
| 20140147402, | |||
| DE102010054918, | |||
| EP829258, | |||
| EP1347736, | |||
| FR2804863, | |||
| GB2207501, | |||
| WO2051369, | |||
| WO2051961, | |||
| WO2009015856, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| Dec 13 2011 | Clariant International Ltd. | (assignment on the face of the patent) | / | |||
| Jun 03 2013 | KLUG, PETER | CLARIANT FINANCE BVI LIMITED | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 030616 | /0338 | |
| Jun 03 2013 | BACK, UTE | CLARIANT FINANCE BVI LIMITED | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 030616 | /0338 | |
| Jun 04 2013 | PILZ, MAURICE FREDERIC | CLARIANT FINANCE BVI LIMITED | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 030616 | /0338 | |
| Aug 28 2015 | CLARIANT FINANCE BVI LIMITED | Clariant International Ltd | ASSIGNMENT OF ASSIGNORS INTEREST SEE DOCUMENT FOR DETAILS | 037212 | /0379 |
| Date | Maintenance Fee Events |
| Sep 04 2020 | M1551: Payment of Maintenance Fee, 4th Year, Large Entity. |
| Nov 04 2024 | REM: Maintenance Fee Reminder Mailed. |
| Date | Maintenance Schedule |
| Mar 14 2020 | 4 years fee payment window open |
| Sep 14 2020 | 6 months grace period start (w surcharge) |
| Mar 14 2021 | patent expiry (for year 4) |
| Mar 14 2023 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Mar 14 2024 | 8 years fee payment window open |
| Sep 14 2024 | 6 months grace period start (w surcharge) |
| Mar 14 2025 | patent expiry (for year 8) |
| Mar 14 2027 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Mar 14 2028 | 12 years fee payment window open |
| Sep 14 2028 | 6 months grace period start (w surcharge) |
| Mar 14 2029 | patent expiry (for year 12) |
| Mar 14 2031 | 2 years to revive unintentionally abandoned end. (for year 12) |